The oxygen evolution reaction (OER) is known as the efficiency-limiting step for the electrochemical cleavage of water mainly due to the large overpotentials commonly used materials on the anode side cause. Since Ni-Fe oxides reduce overpotentials occurring in the OER dramatically they are regarded as anode materials of choice for the electrocatalytically driven water-splitting reaction. We herewith show that a straightforward surface modification carried out with AISI 304, a general purpose austenitic stainless steel, very likely, based upon a dissolution mechanism, to result in the formation of an ultra-thin layer consisting of Ni, Fe oxide with a purity > 99%. The Ni enriched thin layer firmly attached to the steel substrate is responsible for the unusual highly efficient anodic conversion of water into oxygen as demonstrated by the low overpotential of 212 mV at 12 mA/cm 2 current density in 1 M KOH, 269.2 mV at 10 mA/cm 2 current density in 0.1 M KOH respectively. The Ni, Fe-oxide layer formed on the steel creates a stable outer sphere, and the surface oxidized steel samples proved to be inert against longer operating times (> 150 ks) in alkaline medium. In addition Faradaic efficiency measurements performed through chronopotentiometry revealed a charge to oxygen
The cheap stainless commodity steel AISI 304, which basically consists of Fe, Ni, and Cr, was surface-oxidized by exposure to Cl2 gas. This treatment turned AISI 304 steel into an efficient electrocatalyst for water splitting at pH 7 and pH 13. The overpotential of the anodic oxygen evolution reaction (OER), which typically limits the efficiency of the overall water-splitting process, could be reduced to 260 mV at 1.5 mA/cm2 in 0.1 M KOH. At pH 7, overpotentials of 500–550 mV at current densities of 0.65 mA/cm2 were achieved. These values represent a surprisingly good activity taking into account the simplicity of the procedure and the fact that the starting material is virtually omnipresent. Surface-oxidized AISI 304 steel exhibited outstanding long-term stability of its electrocatalytic properties in the alkaline as well as in the neutral regime, which did not deteriorate even after chronopoteniometry for 150 000 s. XPS analysis revealed that surface oxidation resulted in the formation of Fe oxide and Cr oxide surface layers with a thickness in the range of a few nanometers accompanied by enrichment of Cr in the surface layer. Depending on the duration of the Cl2 treatment, the purity of the Fe oxide/Cr oxide mixture lies between 95% and 98%. Surface oxidation of AISI 304 steel by chlorination is an easy and scalable access to nontoxic, cheap, stable, and efficient electrocatalysts for water splitting.
The spin polarization of Pt in Pt/NiFe2O4 and Pt/Fe bilayers is studied by interface-sensitive x-ray resonant magnetic reflectivity to investigate static magnetic proximity effects. The asymmetry ratio of the reflectivity was measured at the Pt L3 absorption edge using circular polarized x-rays for opposite directions of the magnetization at room temperature. The results of the 2% asymmetry ratio for Pt/Fe bilayers are independent of the Pt thickness between 1.8 and 20 nm. By comparison with ab initio calculations, the maximum magnetic moment per spin polarized Pt atom at the interface is determined to be (0.6 ± 0.1) µB for Pt/Fe. For Pt/NiFe2O4 the asymmetry ratio drops below the sensitivity limit of 0.02 µB per Pt atom. Therefore, we conclude, that the longitudinal spin Seebeck effect recently observed in Pt/NiFe2O4 is not influenced by a proximity induced anomalous Nernst effect. In spintronics1 and spin caloritronics 2 pure spin currents can be generated in ferromagnetic insulators (FMIs) by spin pumping 3 , the spin Hall effect 4 and the spin Seebeck effect 5 . Since these spin currents play an important role in spintronic applications, an understanding of the generation, manipulation and detection of spin currents is an important topic of research. A common spin current detection technique uses a nonferromagnetic metal (NM) thin film grown on a ferromagnet (FM). The inverse spin Hall effect 6 converts the spin current into a transverse voltage in the NM. Pt is commonly used as NM due to its large spin Hall angle 7 , but has generated some controversy in the interpretation because of its closeness to the Stoner criterion, which can induce, e.g., Hall or Nernst effects due to the proximity to the FM 8 .For a quantitative evaluation of the spin Seebeck effect (thermal generation of spin currents) one has to exclude or separate various parasitic effects. It is reported 5 that in transverse spin Seebeck experiments a spin current is generated perpendicular to the applied temperature gradient which is typically aligned in-plane. For ferromagnetic metals (FMMs) with magnetic anisotropy, the planar Nernst effect 9 can contribute 10 due to the anisotropic magnetothermopower. Furthermore, out-of-plane temperature gradients due to heat flow into the surrounding area 11 or through the electrical contacts 12 can induce an anomalous Nernst effect (ANE) [13][14][15] or even an unintended longitudinal spin Seebeck effect as recently reported 16 .The longitudinal spin Seebeck effect (LSSE) 17 describes a spin current that is generated parallel to the temperature gradient, which is typically aligned outof-plane to drive the parallel spin current directly into the NM material. For FMMs or semiconducting ferromagnets an ANE can also contribute to the measured voltage 18 . Furthermore, for NM materials close to the Stoner criterion a static magnetic proximity effect in the NM at the NM/FMI interface can lead to a proximity induced ANE 8 . If an in-plane temperature gradient is applied, a proximity induced planar Nernst effect ...
Janus type Water-Splitting Catalysts have attracted highest attention as a tool of choice for solar to fuel conversion. AISI Ni 42 steel was upon harsh anodization converted in a bifunctional electrocatalyst. Oxygen evolution reaction-(OER) and hydrogen evolution reaction (HER) are highly efficiently and steadfast catalyzed at pH 7, 13, 14, 14.6 (OER) respectively at pH 0, 1, 13, 14, 14.6 (HER). The current density taken from long-term OER measurements in pH 7 buffer solution upon the electro activated steel at 491 mV overpotential (η) was around 4 times higher (4 mA/cm 2 ) in comparison with recently developed OER electrocatalysts. The very strong voltagecurrent behavior of the catalyst shown in OER polarization experiments at both pH 7 and at pH 13 were even superior to those known for IrO 2 -RuO 2 . No degradation of the catalyst was detected even when conditions close to standard industrial operations were applied to the catalyst. A stable Ni-, Fe-oxide based passivating layer sufficiently protected the bare metal for further oxidation. Quantitative charge to oxygen-(OER) and charge to hydrogen (HER) conversion was confirmed. High resolution XPS spectra showed that most likely γ−NiO(OH) and FeO(OH) are the catalytic active OER and NiO is the catalytic active HER species.
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